CN111381463B

CN111381463B - Toner and method for producing the same

Info

Publication number: CN111381463B
Application number: CN201911372189.6A
Authority: CN
Inventors: 富永英芳; 田中正健; 桂大侍; 佐藤正道; 琴谷昇平; 山胁健太郎
Original assignee: Canon Inc
Current assignee: Canon Inc
Priority date: 2018-12-28
Filing date: 2019-12-27
Publication date: 2024-04-16
Anticipated expiration: 2039-12-27
Also published as: JP2020106722A; EP3674807B1; CN111381463A; JP7286314B2; US10942466B2; EP3674807A1; US20200209773A1

Abstract

The present invention relates to a toner. A toner comprising toner particles containing a binder resin and an external additive, wherein the toner particles contain a polyvalent metal compound which is at least one selected from the group consisting of an aluminum compound, an iron compound and a magnesium compound, the content of a metal element derived from the polyvalent metal compound in the toner particles is 0.080 to 20.000 mu mol/g, the external additive contains silicone polymer particles having hydroxyl groups, the ratio of the number average particle diameter of the silicone polymer particles to the number average particle diameter of the toner particles is 0.0160 to 0.0650, and the content of the silicone polymer particles is at least 0.10 parts by mass relative to 100.00 parts by mass of the toner particles.

Description

Toner and method for producing the same

Technical Field

The present invention relates to a toner for developing an electrostatic image in an image forming method such as electrophotography and electrostatic printing.

Background

In recent years, demands for copiers and printers have become more diversified, and higher speeds, longer operation lives, higher image quality, and the like have been demanded in various environments. A method of improving durability, chargeability, and fluidity of the toner by externally adding silica particles to the toner particles is adopted. As one example, external addition of silsesquioxane particles (silsesquioxane particles) was investigated as a means of improving such toner performance.

In japanese patent application laid-open No.2018-72389, chargeability is stabilized by externally adding polysiloxane particles composed of a plurality of units to toner particles.

In japanese patent application laid-open No.2017-122873, detachment of silsesquioxane particles is prevented by keeping the particle diameter of the silsesquioxane particles within a specific range and by including a crystalline resin and an amorphous resin in the toner binder resin.

Disclosure of Invention

However, it was found that with the toner of Japanese patent application laid-open No.2018-72389, the silicone particles were detached during long-term use, increasing the risk of fogging.

Further, in japanese patent application laid-open No.2017-122873, it is found that under a high-temperature and high-humidity environment, excessive embedding of silsesquioxane particles and toner cracking occur during long-term use, and there is a risk of contamination of developing members such as a toner bearing member and a developing blade.

The invention provides a toner which can inhibit fog and pollution of components even in long-term use under high-temperature and high-humidity environment.

The present invention relates to a toner comprising:

toner particles containing binder resin, and

The additive agent is added to the mixture of the external additive agent and the water,

wherein the toner particles contain a polyvalent metal compound,

the polyvalent metal compound is at least one selected from the group consisting of an aluminum compound, an iron compound and a magnesium compound,

the content of the metal element derived from the polyvalent metal compound in the toner particles is 0.080. Mu. Mol/g to 20.000. Mu. Mol/g,

the external additive contains silicone polymer particles having hydroxyl groups,

the ratio of the number average particle diameter of the silicone polymer particles to the number average particle diameter of the toner particles is 0.0160 to 0.0650, and

the content of the silicone polymer particles is at least 0.10 parts by mass relative to 100.00 parts by mass of the toner particles.

With the present invention, it is possible to obtain a toner which suppresses fogging and contamination of members even during long-term use under a high-temperature and high-humidity environment.

Further features of the invention will become apparent from the following description of exemplary embodiments.

Detailed Description

Unless otherwise indicated, a description of a numerical range in this invention, such as "above XX and below YY" or "XX to YY", includes values at the upper and lower limits of the range.

The present inventors have found that, as a result of intensive studies, the above problems can be solved with a toner comprising:

Toner particles containing binder resin, and

wherein the toner particles contain a polyvalent metal compound,

The inventors consider that the effects of the present invention are obtained for the following reasons. In the present invention, the silicone polymer particles have hydroxyl groups, and the toner particles contain a specific metal. Therefore, it is considered that hydroxyl groups and metal elements in the silicone polymer particles are electrostatically adsorbed to each other, thereby improving the fixation property of the silicone polymer particles (fixing properties).

It is also considered that if the number average particle diameters of the toner particles and the silicone polymer particles are controlled, contact between the developing member and a portion of the toner particle surface lacking the fixed silicone polymer particles can be prevented, and contamination of the developing member can be suppressed.

The toner particles are described below.

The toner particles contain a polyvalent metal compound, and the polyvalent metal compound is at least one selected from the group consisting of an aluminum compound, an iron compound, and a magnesium compound.

Another feature is that the content of the metal element derived from the polyvalent metal compound in the toner particles is 0.080. Mu. Mol/g to 20.000. Mu. Mol/g, or preferably 0.080. Mu. Mol/g to 14.000. Mu. Mol/g.

Aluminum, iron and magnesium have a relatively strong ionization tendency, and since they are easily ionized, they can be electrostatically adsorbed to the hydroxyl groups of the silicone polymer particles when the content of the metal element is at least 0.080. Mu. Mol/g. However, if the content of the metal element is too high, fogging occurs due to toner charge leakage under a high-temperature and high-humidity environment, and therefore the content of the metal element in the polyvalent metal compound in the toner particles must be 20.000 μmol/g or less.

When two or more polyvalent metal elements are contained, the total content of these metal elements is within the above range.

The method for containing the polyvalent metal compound in the toner particles is not particularly limited. For example, if toner particles are produced by a pulverization method, a polyvalent metal compound may be contained in the raw material resin in advance. The polyvalent metal compound may be added to the toner particles during the melt-kneading of the raw materials.

When toner particles are produced by a wet method such as a polymerization method, the compound may be contained in the raw material or added via an aqueous medium during the production process. From the viewpoint of uniformity, in the wet manufacturing method, it is desirable to include a compound in toner particles by adding the compound in an ionized state in an aqueous medium.

In particular, in the emulsion aggregation method, the polyvalent metal compound may be contained in the toner particles by using the polyvalent metal compound as a flocculant. In this case, the metal ions derived from the polyvalent metal compound are relatively uniformly present in the binder resin. Such metal ions exist not only inside the toner particles but also near the surfaces of the toner particles, which is desirable because it causes the silicone polymer particles to be firmly fixed. The content of the metal element can be measured by the following method.

When the polyvalent metal compound is mixed during manufacture, it may be in the form of a halide, hydroxide, oxide, sulfide, carbonate, sulfate, hexafluorosilyl (hexafluorosilyl) ate, acetate, thiosulfate, phosphate, chlorate, nitrate, or the like. As discussed above, these substances are preferably contained in the toner particles by ionizing them in an aqueous medium and adding them in an ionized state.

The aqueous medium is a medium containing at least 50 mass% of water and 50 mass% or less of a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran.

When the polyvalent metal compound contains aluminum, the aluminum content of the toner particles is preferably 0.080. Mu. Mol/g to 0.400. Mu. Mol/g, or more preferably 0.100. Mu. Mol/g to 0.320. Mu. Mol/g.

When the polyvalent metal compound contains iron, the iron content of the toner particles is preferably 0.250. Mu. Mol/g to 1.250. Mu. Mol/g, or more preferably 0.375. Mu. Mol/g to 1.000. Mu. Mol/g.

When the polyvalent metal compound contains magnesium, the magnesium content of the toner particles is preferably 2.000 to 20.000. Mu. Mol/g, or more preferably 4.000 to 14.000. Mu. Mol/g.

The content of these polyvalent metal elements can be controlled by controlling the addition amount of the polyvalent metal compound at the time of preparing the toner particles. When these polyvalent metal compounds are added from the outside, they can be removed by washing and measurement can be performed.

The reason why the preferable content range of the polyvalent metal element differs depending on the substance is considered to be related to the valence of the metal. That is, when the valence is high, a smaller amount of metal can coordinate with the hydroxyl groups of the silicone polymer particles, thus trivalent aluminum is used in a small amount, divalent magnesium is used in a larger amount, and iron (which may have mixed valence) is used in an intermediate amount. Preferably, the polyvalent metal compound comprises an aluminum compound, and more preferably, the polyvalent metal compound is an aluminum compound.

The toner particles preferably contain an amorphous vinyl resin having an acid value of 1.0mgKOH/g to 40.0mgKOH/g on the surface of the toner particles. The acid value is more preferably 3.0mgKOH/g to 20.0mgKOH/g. If such a resin is present on the surface of the toner particles, deterioration during continuous use is prevented. This is believed to be caused by: partial metal crosslinking occurs due to the presence of acid groups and polyvalent metals on the surface, resulting in improved durability.

The number average particle diameter of the toner particles is preferably 4.0 μm to 10.0 μm, or more preferably 5.0 μm to 9.0 μm.

The external additive used in the present invention is described below.

The external additive contains silicone polymer particles having hydroxyl groups. The silicone polymer having hydroxyl groups is preferably silsesquioxane particles having hydroxyl groups. The silicone polymer particles have an organofunctional group and preferably have a structure represented by (R ^a SiO _3/2 ) _n (wherein R is ^a Is an organofunctional group) are used.

That is, the silicone polymer particles have a structure in which silicon atoms and oxygen atoms are alternately bonded, and the silicone polymer preferably has a structure in which R ^a SiO _3/2 The T3 unit structure is shown.

Furthermore, in the silicone polymer particles ²⁹ In the Si-NMR measurement, the ratio of the area of the peak derived from silicon having a T3 unit structure to the total area of the peaks derived from all silicon elements contained in the silicone polymer particles is preferably 0.90 to 1.00, or more preferably 0.95 to 1.00.

The manner in which the silicone polymer particles have hydroxyl groups is not particularly limited, but there is a method in which the above-mentioned (R ^a SiO _3/2 ) _n Part of (A) is (R) ^a Si(OH)O _2/2 ) Silanol derivatives of silsesquioxane structure are preferred.

For R above ^a Examples include, but are not limited to, C _1-6 (preferably C _1-3 Or more preferably C _1-2 ) Hydrocarbyl (preferably alkyl) and aryl(preferably phenyl).

Silanol derivatives having a silsesquioxane structure can be detected in the toner by pyrolysis GC/MS, for example. The pyrolysis GC/MS measurement method is described below.

In the pyrolysis GC/MS of the silicone polymer particles, the integral value of the peak derived from the cage type silsesquioxane structure represented by the following formula (1) is specified to be 1.000, and the integral value of the peak derived from the cage type silsesquioxane structure silanol derivative represented by the following formula (2) is preferably at least 0.001, or more preferably at least 0.002, or still more preferably at least 0.003. The upper limit is not particularly limited, but is preferably 0.100 or less, or more preferably 0.050 or less, or still more preferably 0.030 or less.

Further, in the present invention, the ratio (B/a) of the number average particle diameter (B) of the silicone polymer particles to the number average particle diameter (a) of the toner particles is 0.0160 to 0.0650. That is, since the silicone polymer particles as the external additive are relatively large with respect to the toner particles, they exert a sufficient spacer effect, and thus it is possible to prevent the portions of the toner particle surfaces lacking the fixed silicone polymer particles from contacting the developing member.

Since embedding of the silicone polymer particles in the toner particle surface can be suppressed, contamination of the developing member can also be suppressed. If the ratio of the number average particle diameters is less than 0.0160, embedding of silicone polymer particles occurs, the toner carrying member is contaminated, and streaks appear on the developing blade.

If the ratio of the number average particle diameters exceeds 0.0650, the silicone polymer particles are detached and fogging occurs. The ratio is preferably 0.0200 to 0.0500.

The number average particle diameter of the silicone polymer particles is preferably 120nm to 350nm, or more preferably 150nm to 300nm. If the number average particle diameter is at least 120nm, the transferability can be further improved. If it is 350nm or less, fogging can be further suppressed.

The content of the silicone polymer particles is preferably at least 0.10 parts by mass with respect to 100.00 parts by mass of the toner particles. If the content is at least 0.10 parts by mass, the effect of the present invention can be achieved. If it is less than 0.10 parts by mass, contamination of the member occurs, and transferability also decreases. The content is preferably 0.10 parts by mass to 5.00 parts by mass with respect to 100.00 parts by mass of the toner particles.

The content of the metal element derived from the polyvalent metal compound is preferably 10. Mu. Mol to 5000. Mu. Mol with respect to 1g of the silicone polymer particles. Within this range, the silicone polymer particles are more easily fixed to the toner particle surface. A range of 10. Mu. Mol to 1000. Mu. Mol relative to 1g of the silicone polymer particles is more preferable, and a range of 20. Mu. Mol to 400. Mu. Mol relative to 1g of the silicone polymer particles is still more preferable.

The method for producing the silanol derivative having a silsesquioxane structure is not particularly limited, but, for example, the following methods are preferable.

Will contain R bonded to the same silicon atom ^a And 3 reactive groups (halogen atom, hydroxyl group, acetoxy group or alkoxy group) (hereinafter referred to as trifunctional silane) are added to the aqueous medium.

When hydrolysis reaction and condensation reaction are performed with trifunctional silane dissolved or dispersed in an aqueous medium, various organosilicon polymer compounds are produced, and as one of these compounds, silanol derivative compounds having a silsesquioxane structure are obtained. The amount of silanol derivative structure (amount of hydroxyl groups) can be controlled, for example, by controlling hydrolysis and addition polymerization of trifunctional silane, and specifically, by controlling reaction temperature, reaction time, and reaction solvent, and pH, drying temperature, and drying time.

The organosilicon compound used as a precursor of the silanol derivative compound having a silsesquioxane structure is described below.

The silanol derivative compound having a silsesquioxane structure is preferably a polycondensate of an organosilicon compound having a structure represented by the following formula (Z).

(in the formula (Z), R ^a Represents an organofunctional group, and R ¹ 、R ² And R is ³ Each independently represents a halogen atom, a hydroxy group or an acetoxy group, or (preferably C _1-3 ) An alkoxy group).

R ^a Is an organic functional group without any particular limitation, but preferred examples include C _1-6 (preferably C _1-3 More preferably C _1-2 ) Hydrocarbyl (preferably alkyl) and aryl (preferably phenyl).

R ¹ 、R ² And R is ³ Each independently represents a halogen atom, a hydroxyl group, an acetoxy group or an alkoxy group. These are reactive groups that form a crosslinked structure by hydrolysis, addition polymerization, and condensation. R can be controlled by means of reaction temperature, reaction time, reaction solvent and pH ¹ 、R ² And R is ³ Hydrolysis, addition polymerization and condensation of (a).

Examples of formula (Z) include the following:

trifunctional methylsilanes such as p-styryltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, and methyldiethoxyhydroxysilane; trifunctional ethylsilanes such as ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, and ethyltrihydroxysilane; trifunctional propyl silanes such as propyl trimethoxysilane, propyl triethoxysilane, propyl trichlorosilane, propyl triacetoxysilane, and propyl trihydroxy silane; trifunctional butylsilanes such as butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, and butyltrihydroxysilane; trifunctional hexylsilanes such as hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, and hexyltrihydroxysilane; and trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane. These organosilicon compounds may be used alone, or two or more kinds may be used in combination.

The following compounds may also be used in combination with an organosilicon compound having a structure represented by the formula (Z): an organosilicon compound having 4 reactive groups in a molecule (tetrafunctional silane), an organosilicon compound having 2 reactive groups in a molecule (difunctional silane), and an organosilicon compound having 1 reactive group in a molecule (monofunctional silane). Examples include:

dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3- (2-aminoethyl) aminopropyl trimethoxysilane, 3- (2-aminoethyl) aminopropyl triethoxysilane, and trifunctional vinylsilanes, such as vinyltriisocyanato silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinylethoxydihydroxysilane, vinyldimethoxyhydroxysilane, vinylethoxymethoxyhydroxysilane, and vinyldiethoxyhydroxysilane.

The content of the structure represented by the formula (Z) in the silicone polymer-forming monomer is preferably at least 50mol%, or more preferably at least 60mol%.

[ method for producing toner particles ]

As a method for producing toner particles, a known method such as a kneading pulverization method or a wet production method can be used. Wet methods are preferred for obtaining uniform particle size and controlling particle shape. Examples of the wet production method include a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, and the like, and the emulsion aggregation method is preferable. This is because the polyvalent metal element is more easily ionized in the aqueous medium, and also because the polyvalent metal element is more easily contained in the toner particles when the binder resin is aggregated.

In the emulsion aggregation method, a dispersion is first prepared from a material containing fine particles of a binder resin and, if necessary, fine particles of a colorant. It is also possible to add a dispersion stabilizer to the dispersion of the resulting material, then disperse it and mix it. A flocculant is then added to aggregate the mixture until the desired toner particle size is achieved, and the resin particles are also fused together after or during aggregation. In this method, shape control by heating may also be performed as needed, thereby forming toner particles.

Here, the fine particles of the binder resin may be composite particles formed into a multi-layered particle including two or more layers composed of different resins. This can be produced, for example, by emulsion polymerization, microemulsion polymerization, inversion emulsion, or the like, or by a combination of a plurality of production methods.

When the toner particles contain an internal additive, the internal additive may be contained in the resin fine particles. It is also possible to separately prepare a dispersion of internal additive fine particles composed only of the internal additive, and then it is possible to aggregate the internal additive fine particles with the resin fine particles. It is also possible to add resin fine particles having different compositions at different times during aggregation and aggregate them, thereby preparing toner particles composed of layers having different compositions.

[ Dispersion stabilizer ]

The following may be used as dispersion stabilizers:

inorganic dispersion stabilizers such as tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina.

Other examples include organic dispersion stabilizers such as polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium carboxymethyl cellulose, and starch.

As the surfactant, a known cationic surfactant, anionic surfactant or nonionic surfactant can be used.

Specific examples of the cationic surfactant include dodecylammonium bromide, dodecyltrimethylammonium bromide, dodecylpyridinium chloride, dodecylpyridinium bromide, hexadecyltrimethylammonium bromide, and the like.

Specific examples of the nonionic surfactant include dodecyl polyoxyethylene ether, cetyl polyoxyethylene ether, nonylphenyl polyoxyethylene ether, lauryl polyoxyethylene ether, sorbitan monooleate polyoxyethylene ether, styrylphenyl polyoxyethylene ether, and monodecanoyl sucrose, and the like.

Specific examples of the anionic surfactant include aliphatic soaps such as sodium stearate and sodium laurate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene (2) lauryl ether sulfate, and the like.

[ Binder resin ]

The binder resin constituting the toner particles is described below.

Preferable examples of the binder resin include vinyl-based resins, polyester resins, and the like. Examples of vinyl resins, polyester resins, and other binder resins include the following resins and polymers:

homopolymers of styrene and substituted styrenes, such as polystyrene and polyvinyltoluene; styrene-based copolymers such as styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, and styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resins, polyamide resins, epoxy resins, polyacrylic resins, rosin, modified rosin, terpene resins, phenolic resins, aliphatic or alicyclic hydrocarbon resins, and aromatic petroleum resins.

The binder resin preferably contains a vinyl-based resin, and more preferably contains a styrene-based copolymer. These binder resins may be used alone or mixed together.

The binder resin preferably contains a carboxyl group, and is preferably a resin produced using a polymerizable monomer containing a carboxyl group. Examples include vinyl carboxylic acids such as acrylic acid, methacrylic acid, alpha-ethacrylic acid, and crotonic acid; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid; and unsaturated dicarboxylic acid monoester derivatives such as monoacryloxyethyl succinate, monomethacryloxyethyl succinate, monoacryloxyethyl phthalate, and monomethacryloxyethyl phthalate.

As the polyester resin, polycondensates of the carboxylic acid component and the alcohol component listed below can be used. Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid. Examples of the alcohol component include bisphenol a, hydrogenated bisphenol, bisphenol a ethylene oxide adducts, bisphenol a propylene oxide adducts, glycerol, trimethylolpropane, and pentaerythritol.

The polyester resin may be a urea group-containing polyester resin. Preferably, the ends and other carboxyl groups of the polyester resin are not terminated.

[ Cross-linking agent ]

In order to control the molecular weight of the binder resin constituting the toner particles, a crosslinking agent may also be added during the polymerization of the polymerizable monomer.

Examples include ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1, 3-butanediol diacrylate, 1, 4-butanediol diacrylate, 1, 5-pentanediol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diacrylates of polyethylene glycol #200, #400 and #600, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester diacrylate (MANDA, nippon Kayaku co., ltd.) wherein methacrylates are used in place of acrylates.

The amount of the crosslinking agent to be added is preferably 0.001 parts by mass to 15.000 parts by mass relative to 100 parts by mass of the polymerizable monomer.

[ Release agent ]

The toner particles may also contain a release agent. In particular, using an ester wax having a melting point in the range of 60 ℃ to 90 ℃, a plasticizing effect is easily obtained because the wax is highly compatible with the binder resin, and the silicone polymer particles can be effectively fixed to the toner particles.

Examples of the ester wax include waxes mainly composed of fatty acid esters, such as carnauba wax and montan acid ester wax; fatty acid esters in which an acid component is partially deacidified or completely deacidified, such as deacidified carnauba wax; methyl ester compounds containing hydroxyl groups obtained by hydrogenation of vegetable matter oils and fats; saturated fatty acid monoesters such as stearyl stearate and behenyl behenate; diester compounds of saturated aliphatic dicarboxylic acids with saturated aliphatic alcohols, such as distearyl sebacate, distearyl dodecanedioate and distearyl octadecanedioate; and di-esters of saturated aliphatic diols with saturated aliphatic monocarboxylic acids, such as nonyleneglycol dibehenate and dodecylglycol distearate.

Among these waxes, it is desirable to include difunctional ester waxes (diesters) having two ester bonds in the molecular structure.

The difunctional ester wax is an ester compound of a dihydric alcohol and an aliphatic monocarboxylic acid or an ester compound of a dicarboxylic acid and an aliphatic monohydric alcohol.

Specific examples of aliphatic monocarboxylic acids include myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, cerotic acid, montanic acid, melissic acid, oleic acid, iso-oleic acid, linoleic acid and linolenic acid.

Specific examples of the aliphatic monohydric alcohol include myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, ceryl alcohol, octaceryl alcohol, and triacontyl alcohol.

Specific examples of dicarboxylic acids include succinic acid (succinic acid), glutaric acid (pentanedioic acid), adipic acid (hexanedioic acid) (adipic acid)), pimelic acid (heptanedioic acid), suberic acid (pimelic acid), suberic acid (suberic acid), azelaic acid (azelaic acid), sebacic acid (decanedioic acid), sebacic acid (sebasic acid), dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like.

Specific examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 10-decanediol, 1, 12-dodecanediol, 1, 14-tetradecanediol, 1, 16-hexadecanediol, 1, 18-octadecanediol, 1, 20-eicosanediol, 1, 30-triacontanediol, diethylene glycol, dipropylene glycol, 2, 4-trimethyl-1, 3-pentanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol, spiroglycol, 1, 4-phenylene glycol, bisphenol A, hydrogenated bisphenol A, and the like.

Other mold release agents that may be used include petroleum-based waxes such as paraffin wax, microcrystalline wax and vaseline and their derivatives, montan wax and its derivatives, hydrocarbon waxes obtained by the Fischer-Tropsch process and their derivatives, polyolefin waxes such as polyethylene and polypropylene and their derivatives, natural waxes such as carnauba wax and candelilla wax and their derivatives, higher aliphatic alcohols, and fatty acids such as stearic acid and palmitic acid.

The content of the release agent is preferably 5.0 parts by mass to 20.0 parts by mass with respect to 100.0 parts by mass of the binder resin.

[ colorant ]

The toner may further contain a colorant. The colorant is not particularly limited, and the following known colorants can be used.

Examples of the yellow pigment include iron oxide yellow, naples yellow (Naples yellow), naphthol yellow S, hansa yellow G (Hansa yellow G), hansa yellow 10G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG (permanent yellow NCG), condensed azo compounds such as tartrazine lake, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include:

c.i. pigment yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168 and 180.

Examples of red pigments include iron oxide red, permanent red 4R, lithol red, pyrazolone red, lake red calcium salt (watching red calcium salt), lake red C, lake red D, brilliant carmine 6B, brilliant carmine 3B, eosin lake, rhodamine lake B, condensed azo compounds such as alizarin lake, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include:

c.i. pigment red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254.

Examples of blue pigments include basic blue lake, victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, fast sky blue (fast sky blue), copper phthalocyanine compounds such as indanthrene blue BG (indathrene blue BG) and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specific examples include:

c.i. pigment blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66.

Examples of the black pigment include carbon black and aniline black. These colorants may be used alone, as a mixture, or as a solid solution.

The content of the colorant is preferably 3.0 parts by mass to 15.0 parts by mass with respect to 100.0 parts by mass of the binder resin.

[ Charge control agent ]

The toner particles may also contain a charge control agent. Well known charge control agents may be used. A charge control agent that provides a fast charging speed and can stably maintain a uniform charging amount is particularly desirable.

Examples of the charge control agent for controlling the negative chargeability of the toner particles include:

organic metal compounds and chelating compounds, including monoazo metal compounds, acetylacetonate metal compounds, aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, and hydroxycarboxylic and dicarboxylic acid-based metal compounds. Other examples include aromatic hydroxycarboxylic acids, aromatic monocarboxylic and polycarboxylic acids and their metal salts, anhydrides and esters, and phenol derivatives such as bisphenol. Other examples include urea derivatives, metal-containing salicylic acid-based compounds, metal-containing naphthoic acid-based compounds, boron compounds, quaternary ammonium salts, and calixarenes.

Meanwhile, examples of the charge control agent for controlling the positively chargeable property of the toner particles include: nigrosine and nigrosine modified with fatty acid metal salts; a guanidine compound; an imidazole compound; quaternary ammonium salts such as tributylbenzyl ammonium-1-hydroxy-4-naphthalene sulfonate and tetrabutylammonium tetrafluoroborate, onium salts such as phosphonium salts as analogues of these, and lake pigments of these; triphenylmethane dyes and lake pigments thereof (using phosphotungstic acid, phosphomolybdic acid, phosphotungstic acid, tannic acid, lauric acid, gallic acid, ferricyanic acid or ferrocyanide compounds, etc. as fixing agents); metal salts of higher fatty acids; and a resin-based charge control agent.

A single one of these charge control agents, or a combination of two or more thereof may be used. The addition amount of these charge control agents is preferably 0.01 to 10.00 parts by mass with respect to 100.00 parts by mass of the binder resin.

The following describes a method for measuring various physical properties of the toner of the present invention.

< number average particle diameter of toner particles and Silicone Polymer particles >

The number average particle diameters of the toner particles and the silicone polymer particles were measured using an "S-4800" scanning electron microscope (Hitachi, ltd.). The toner having the externally added silicone polymer was observed, the long diameters of the primary particles of 100 randomly selected silicone polymer particles were measured in a field of view enlarged to a maximum magnification of 50,000 x, and the number average particle diameter was calculated. The observation magnification is appropriately adjusted according to the size of the silicone polymer particles.

For the toner particles, the long diameters of 100 randomly selected toner particles were measured in a field of view enlarged to a magnification of 2,000×and the number average particle diameter was calculated.

When the raw silicone polymer particles before external addition are available, they are used to calculate the number average particle size.

< analysis of Silicone Polymer particles and silanol derivative Structure in Silicone Polymer particles >

A ratio of peak areas of T3 unit structures in the silicone polymer particles contained in the toner was determined using a pyrolysis gas chromatograph mass spectrometer (hereinafter referred to as pyrolysis GC/MS) and NMR, and silanol derivative structures (R ^a Si(OH)O _2/2 )。

When the toner contained a silicon-containing material other than the silicone polymer particles, 1g of the toner was dissolved and dispersed in 31g of chloroform in a vial. The dispersion was carried out using an ultrasonic homogenizer for 30 minutes, thereby preparing a dispersion liquid.

An ultrasonic processing unit: VP-050 ultrasonic homogenizer (manufactured by Taitec Corporation).

Microchip: step microchip (front end diameter)

Microchip front end position: the central portion of the glass vial was 5mm above the bottom surface of the vial

Ultrasonic conditions: intensity 30%,30 min; ultrasonic waves were applied while cooling the vials with ice water so that the temperature of the dispersion did not rise.

The dispersion was transferred to a glass tube (50 ml) for a swing rotor, and centrifuged (H-9R; manufactured by Kokusan Co.Ltd.) at 58.33S ^-1 And centrifugally separated for 30 minutes. After centrifugal separation, the glass tube contains therein a silicon-containing material other than the silicone polymer particles, and a separated residue obtained by removing the silicon-containing material other than the silicone polymer particles from the toner. The residue obtained by removing the silicon-containing materials other than the silicone polymer particles from the toner was extracted, and chloroform was removed by vacuum drying (40 ℃/24 hours), thereby preparing a sample.

The sample or raw silicone polymer particles were then used to analyze the silicone polymer particles by pyrolysis GC/MS.

The silanol derivative structure can be identified by analyzing mass spectra of components derived from decomposition products of the silanol derivative structure generated when a sample or silicone polymer particles are pyrolyzed at about 550 ℃ to 700 ℃.

[ pyrolysis GC/MS measurement conditions ]

Pyrolysis unit: JPS-700 (Japan Analytical Industry Co.Ltd.)

Decomposition temperature: 590 DEG C

GC/MS unit: focus GC/ISQ (ThermoFisher)

Column: HP-5Ms, length 60m, inner diameter 0.25mm, film thickness 0.25 μm

Injection port temperature: 200 DEG C

Flow pressure: 100kPa

Split (spilt): 50ml/min

MS ionization: EI (electronic equipment)

Ion source temperature: 200 ℃ and mass range of 45-650

In the above measurement, the integral value of the peak derived from the cage-type silsesquioxane structure represented by the above formula (1) was defined as 1.000, and the integral value of the peak derived from the silanol derivative of the cage-type silsesquioxane structure represented by the above formula (2) was calculated.

Then pass through the solid ²⁹ Si-NMR is used to measure and calculate the ratio of the amount of the constituent compounds of the identified silicone polymer particles present and the ratio of the T3 unit structures in the silicone polymer particles.

In solid form ²⁹ In Si-NMR, peaks are detected in different displacement regions according to the structure of functional groups bonded to Si constituting the silicone polymer.

Standard samples can be used to specify the structure bonded to Si at each peak. The ratio of the amounts of the constituent compounds present can also be calculated from the peak areas obtained. The ratio of the peak area of the T3 cell structure to the total peak area can also be determined by calculation.

Solid body ²⁹ The measurement conditions of Si-NMR are as follows, for example.

A unit: JNM-ECX5002 (JEOL RESONANCE Inc.)

Temperature: room temperature

The measuring method comprises the following steps: the DDMAS method is used for solving the problems of the prior art, ²⁹ Si 45°

sample tube: zirconia 3.2mm

Sample: filling the sample tube with a powder

Sample rotation speed: 10kHz

Relaxation delay: 180s

Scanning: 2000

After this measurement, peaks of a plurality of silane components having different substituents and linking groups in the silicone polymer particles were separated into the following X1, X2, X3 and X4 structures by curve fitting, and each peak area was calculated.

Note that the X3 structure mentioned below corresponds to a T3 unit structure in the present invention.

X1 structure: (Ri) (Rj) (Rk) SiO _1/2 (A1)

X2 structure: (Rg) (Rh) Si (O) _1/2 ) ₂ (A2)

X3 structure: rmSi (O) _1/2 ) ₃ (A3)

X4 structure: si (O) _1/2 ) ₄ (A4)

By passing through ¹³ C-NMR to confirm the above R ^a A hydrocarbon group represented.

<< ¹³ C-NMR (solid) measurement conditions>>

A unit: JNM-ECX500II (JEOL RESONANCE Inc.)

Sample tube: 3.2mm

Sample: filling the sample tube with a powder

Sample temperature: room temperature

Pulse mode: CP/MAS

Measuring nuclear frequency: 123.25MHz # ¹³ C)

Standard substance: adamantane (external standard 29.5 ppm)

Sample rotation speed: 20kHz

Contact time: 2ms

Delay time: 2s

Cumulative number of times: 1024 times

In this method, attribution-basedIn methyl groups bound to silicon atoms (Si-CH ₃ ) Ethyl (Si-C) ₂ H ₅ ) Propyl (Si-C) ₃ H ₇ ) Butyl (Si-C) ₄ H ₉ ) Amyl (Si-C) ₅ H ₁₁ ) Hexyl (Si-C) ₆ H ₁₃ ) Or phenyl (Si-C) ₆ H ₅ The presence or absence of a signal of (-) is confirmed by R above ^a A hydrocarbon group represented.

< determination of Silicone Polymer particles contained in toner >

The content of the silicone polymer particles in the toner can be determined by the following method.

Microchip: step microchip, front end diameter

The above procedure was repeated to prepare 4g of dried samples. This was granulated, and the silicon content was determined by fluorescent X-rays.

Fluorescent X-ray measurement was carried out in accordance with JIS K0119-1969, concretely as follows.

As the measurement unit, an "Axios" wavelength dispersive fluorescent X-ray spectrophotometer (manufactured by PANalytical) and an attached "SuperQ ver.5.0l" dedicated software (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data were used. The Rh anode was used for an X-ray tube and vacuum was used as a measurement atmosphere, and the measurement diameter (collimator mask diameter (collimator mask diameter)) was 27mm.

Elements in the range of F to U were measured by Omnian method, and detected with a Proportion Counter (PC) for light elements and a Scintillation Counter (SC) for heavy elements. The acceleration voltage and current values of the X-ray generator were set so that the output was 2.4kW. For the measurement samples, 4g of the samples were placed in a special aluminum press ring, flattened, and then pressed for 60 seconds at 20MPa using a "BRE-32" tablet press shaper (manufactured by Maekawa Testing Machine mfg.co., ltd.) to form pellets having a thickness of 2mm and a diameter of 39 mm.

The measurement was performed under the above conditions so that the elements were identified based on their peak positions in the resulting X-rays, and the mass ratio of the elements was calculated from the count rate (unit: cps) as the number of X-ray photons per unit time.

For analysis, the mass ratio of all elements contained in the sample was calculated by FP assay, and the silicon content of the toner was determined. In the FP method, the remaining amount is set according to the binder resin of the toner.

The silicon content of the toner and its structure can be determined by fluorescence X-ray through a solid ²⁹ The content of the silicone polymer particles in the toner is calculated from the relationship between the content ratio of silicon in the constituent compounds of the silicone polymer particles specified by SiNMR and pyrolytic GC/MS.

< content of polyvalent Metal element in toner particles (ICP-AES) >)

The content of the polyvalent metal element in the toner particles was measured using an inductively coupled plasma atomic emission spectrometer (ICP-AES; manufactured by Seiko Instruments, inc.).

As a pretreatment, 100.0mg of toner particles were acid-degraded with 8.00ml of 60% nitric acid (for atomic absorption analysis, manufactured by Kanto Chemical Co., inc.).

Acid degradation was performed in a sealed container at an internal temperature of 220 ℃ for 1 hour using an ETHOS 1600 high efficiency microwave digestion system (Milestone General k.) to prepare a sample solution containing a polyvalent metal element.

Then, ultrapure water was added to a total of 50.00g, thereby obtaining a measurement sample. A calibration curve was prepared for the polyvalent metal element, and the amount of metal contained in each sample was measured. Samples prepared by adding ultrapure water to 8.00ml of nitric acid to a total of 50.00g were also measured as a blank, and the metal amount of the blank was subtracted.

< acid value of resin >

The acid number is the mg of potassium hydroxide required to neutralize the acid contained in 1g of the sample. The acid value was measured according to JIS K0070-1992, specifically by the following procedure.

Titration was performed with 0.1mol/L potassium hydroxide ethanol solution (manufactured by Kishida Chemical Co. Ltd.). The factor of the potassium hydroxide ethanol solution can be determined by a potentiometric titration apparatus (AT-510 automatic potentiometric titration apparatus; manufactured by Kyoto Electronics Manufacturing Co.Ltd.). 100ml of 0.100mol/L hydrochloric acid was taken in a 250ml high-type beaker and titrated with potassium hydroxide ethanol solution, and the amount of potassium hydroxide ethanol solution required for neutralization was determined. 0.100mol/L hydrochloric acid was prepared in accordance with JIS K8001-1998.

The measurement conditions for acid value measurement are shown below.

Titration unit: AT-510 potentiometric titration device (manufactured by Kyoto Electronics manufacturing. Co. Ltd.)

An electrode: double-junction composite glass electrode (Double-junction type composite glass electrode) (manufactured by Kyoto Electronics manufacturing. Co. Ltd.)

Titration unit control software: AT-WIN

Titration analysis software: tview (Tview)

Titration parameters and control parameters during titration were set as follows.

(titration parameters)

Titration mode: blank titration

Titration mode: full titration

Maximum titration amount: 20ml of

Waiting time before titration: 30 seconds

Titration direction: automatic machine

(control parameters)

Endpoint determination potential: 30dE

Endpoint determination potential value: 50dE/dml

And (3) end point detection and judgment: not set for

Control speed mode: standard of

Gain: 1

Data collection potential: 4mV

Data collection titration amount: 0.1ml

Main test

0.100g of the measurement sample was accurately weighed into a 250ml high-type beaker, 150ml of a mixed solution of toluene/ethanol (3:1) was added, and the sample was dissolved over 1 hour. The above potentiometric titration apparatus was then used to titrate it with the above potassium hydroxide ethanol solution.

Blank test

Titration was performed by the above procedure except that no sample was used (i.e., only a mixed toluene: ethanol solution (3: 1)) was used.

The result was then substituted into the following formula, whereby the acid value was calculated:

A＝[(C-B)×f×5.611]/S

(wherein A is an acid value (mg KOH/g), B is an addition amount (ml) of the potassium hydroxide ethanol solution in the blank test, C is an addition amount (ml) of the potassium hydroxide ethanol solution in the main test, f is a coefficient of the potassium hydroxide solution, and S is a mass (g) of the sample).

< measurement of weight average particle diameter (D4) of toner particles >

The particle diameter of the toner particles can be measured by a pore resistance method. For example, the particle size of the toner particles can be measured and calculated using "Multisizer3 Coulter Counter" together with the accompanying proprietary Multisizer 3version 3.51 software (manufactured by Beckman Coulter Inc.).

A "Multisizer (R) 3 Coulter Counter" precision particle size distribution analyzer (Beckman Coulter, inc.) based on the pore resistance method was used with dedicated "Beckman Coulter Multisizer 3 Version 3.51" software (Beckman Coulter, inc.). The measurement was performed using 25,000 effective measurement channels using a pore size of 100 μm, and the measurement data was analyzed to calculate the particle size.

For example, the aqueous electrolyte solution used for measurement may be a solution of extra sodium chloride dissolved in ion-exchanged water to a concentration of about 1 mass%, such as "ISOTON II" (Beckman Coulter, inc.). The following settings were made on dedicated software prior to measurement and analysis.

On the "change standard measurement method (SOM)" interface of the dedicated software, the total count in the control mode was set to 50000 particles, the number of measurements was set to 1, and the Kd value was set to a value obtained using "standard particle 10.0 μm" (Beckman Coulter, inc.). The threshold and noise level are automatically set by pressing a threshold/noise level measurement button. The current was set to 1600 μa, the gain was set to 2, and the electrolyte solution was set to ISOTON II, and the post-measurement oral tube irrigation check was entered.

On the "pulse-to-particle diameter conversion setting" interface of the dedicated software, the element interval was set to logarithmic particle diameter, the particle diameter elements were set to 256, and the particle diameter range was set to 2 μm to 60 μm.

The specific measurement method is as follows.

(1) About 200mL of the aqueous electrolyte solution was added to a 250mL glass round bottom beaker dedicated to Multisizer 3, the beaker was set on a sample stand and stirred with a stirring bar counter clockwise at 24 rps. Contaminants and air bubbles within the oral tubing are then removed by the "oral tubing flush" function of the dedicated software.

(2) 30mL of the above electrolyte aqueous solution was placed in a 100mL glass-made flat bottom beaker, and about 0.3mL of a dilution liquid for diluting "Contaminon N" (10 mass% aqueous solution of neutral cleaning agent for precision instrument cleaning, wako Pure Chemical Industries, ltd.) with ion-exchanged water by 3-fold mass was added.

(3) A predetermined amount of ion-exchanged water and about 2mL of conteminon N were added to a water tank equipped with two built-in oscillators 180 ° out of phase with each other, an oscillation frequency of 50kHz, and an ultrasonic disperser "Ultrasonic Dispersion System Tetra" (Nikkaki Bios co., ltd.) with an electric power output of 120W.

(4) The beaker of the above (2) was set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser was started. The height position of the beaker was adjusted to maximize the resonance state of the liquid surface of the electrolyte aqueous solution in the beaker.

(5) The aqueous electrolyte solution in the beaker of the above (4) was exposed to ultrasonic waves while about 10mg of toner (particles) was added little by little to the aqueous electrolyte solution and dispersed. The ultrasound was then dispersed for a further 60 seconds. During ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to 10 ℃ to 40 ℃.

(6) The aqueous electrolyte solution of the above (5) in which the toner (particles) was dispersed was pipetted dropwise into the round-bottomed beaker of the above (1) provided on the sample stage, and adjusted to a measured concentration of about 5%. The measurement was then carried out until the number of particles measured reached 50000.

(7) The measurement data are analyzed by dedicated software attached to the apparatus, and the weight average particle diameter is calculated (D4). The weight average particle diameter (D4) is the "average diameter" at the interface of analysis/volume statistics (arithmetic mean) when the graph/volume% is set in the dedicated software.

Examples

The present invention will be described in more detail below based on examples and comparative examples, but the present invention is by no means limited to these. Unless otherwise indicated, the parts in the examples are based on mass.

< preparation of resin particle Dispersion 1 >

78.0 parts of styrene, 20.7 parts of butyl acrylate, 1.3 parts of acrylic acid as a monomer for providing a carboxyl group and 3.2 parts of n-lauryl mercaptan were mixed and dissolved. An aqueous solution of 1.5 parts of Neogen RK (manufactured by DKS co., ltd.) in 150 parts of ion-exchanged water was then added to the solution and dispersed.

Then, it was slowly stirred for 10 minutes while adding an aqueous solution of 0.3 part of potassium persulfate in 10 parts of ion-exchange water. After nitrogen purging, emulsion polymerization was carried out at 70 ℃ for 6 hours. After completion of the polymerization, the reaction liquid was cooled to room temperature, and ion-exchanged water was added, thereby obtaining a resin particle dispersion 1 having a solid content concentration of 12.5 mass% and a volume-based median particle diameter of 0.2 μm.

To measure the acid value, a part of the obtained resin particles 1 was washed with pure water to remove the surfactant, and dried under reduced pressure. The acid value of the resin was measured and confirmed to be 9.5mg KOH/g.

< preparation of resin particle Dispersion 2 >

Resin particle dispersion 2 was obtained in the same manner as resin particle dispersion 1 except that the amount of butyl acrylate was changed to 21.6 parts and the amount of acrylic acid was changed to 0.4 parts. The median particle diameter of the volume-based resin particle dispersion 2 obtained was 0.2. Mu.m, and the acid value of the resin was confirmed to be 3.0mg KOH/g.

< preparation of resin particle Dispersion 3 >

Resin particle dispersion 3 was obtained in the same manner as resin particle dispersion 1, except that the amount of butyl acrylate was changed to 17.5 parts and the amount of acrylic acid was changed to 4.5 parts. The median particle diameter of the resultant resin particle dispersion 3 on a volume basis was 0.2. Mu.m, and the acid value of the resin was confirmed to be 38.0mg KOH/g.

< preparation of Silicone Polymer particles 1>

< step 1>

360 parts of water was placed in a reaction vessel equipped with a thermometer and a stirrer, and 17 parts of 5.0 mass% hydrochloric acid was added, thereby obtaining a uniform solution. This was stirred at 25℃while 136 parts of methyltrimethoxysilane was added thereto, stirred for 5 hours, and then filtered, thereby obtaining a clear reaction solution containing a silanol compound or a partial condensate thereof.

< step 2>

540 parts of water was placed in a reaction vessel equipped with a thermometer, a stirrer and a dropwise adding device, and 19 parts of 10.0 mass% aqueous ammonia was added, thereby obtaining a uniform solution. It was stirred at 30℃while 100 parts of the reaction solution obtained in step 1 was added dropwise over 0.33 hours, followed by stirring for 6 hours, thereby obtaining a suspension. The resulting suspension was centrifugally separated to precipitate and take out fine particles, which were then dried in a dryer at 180 ℃ for 24 hours, thereby obtaining silicone polymer particles 1.

Pyrolytic GC/MS and NMR of the organosilicon polymer particles 1 showed that they were silanol derivatives having a silsesquioxane structure. The number average particle diameter of the primary particles was 150nm. The physical properties are shown in table 1.

< preparation of Silicone Polymer particles 2 to 9 >

The silicone polymer particles 2 to 9 were obtained as in the production example of the silicone polymer particle 1, except that the addition amount of the catalyst, the dropping time, and the like were changed as shown in table 1. The physical properties are shown in table 1.

TABLE 1

< preparation of Release agent Dispersion >

100 parts of a release agent (behenate, melting point 72.1 ℃) and 15 parts of Neogen RK were mixed with 385 parts of ion-exchanged water, and dispersed with a wet jet mill unit JN100 (Jokoh co., ltd.) for about 1 hour, to obtain a release agent dispersion. The solid content concentration of the release agent dispersion was 20 mass%.

< preparation of colorant Dispersion >

100 parts of carbon black "Nipex35 (Orion Engineered Carbons)" and 15 parts of Neogen RK as colorants were mixed with 885 parts of ion-exchanged water, and dispersed in the wet jet mill unit JN100 for about 1 hour, thereby obtaining a colorant dispersion.

< toner 1 preparation example >

< preparation example of toner particle 1 >

265 parts of the resin particle dispersion 1, 10 parts of the release agent dispersion and 10 parts of the colorant dispersion were dispersed with a homogenizer (IKAULTRA-Turrax T50; manufactured by IKAJapan K.K.). This was stirred while the temperature in the vessel was adjusted to 30℃and 1mol/L aqueous sodium hydroxide solution was added to adjust the pH to 8.0.

An aqueous solution of 0.08 part of aluminum chloride dissolved in 10 parts of ion-exchanged water was added as a flocculant at 30 ℃ for 10 minutes under stirring. It was allowed to stand for 3 minutes before starting the temperature rise, and the temperature was raised to 50 ℃ to generate aggregated particles. In this state with a "Multisizer ^TM The particle size of the aggregated particles was measured by 3 Coulter Counter "(manufactured by Beckman Coulter Inc.). When the weight average particle diameter reached 7.2 μm, 0.9 parts of sodium chloride and 5.0 parts of Neogen RK were added to stop the particle growth.

1mol/L aqueous sodium hydroxide solution was added to adjust the pH to 9.0, and then the temperature was raised to 95℃to spheroidize the aggregated particles. When the average circularity reached 0.980, cooling was started, and the mixture was cooled to room temperature, thereby obtaining toner particle dispersion liquid 1.

Hydrochloric acid was added to the obtained toner particle dispersion liquid 1 so as to adjust the pH to 1.5 or less, and the dispersion liquid was stirred for one hour, left to stand, and subjected to solid-liquid separation with a pressure filtration unit, thereby obtaining a toner cake. This was reslurried with ion-exchanged water to obtain a dispersion again, and then solid-liquid separation was performed with the same filtration unit. The repulping and solid-liquid separation were repeated until the conductivity of the filtrate was 5.0 μs/cm or less, and then final solid-liquid separation was performed, thereby obtaining a toner cake. The obtained toner cake was dried, and then classified with a classifier, thereby obtaining toner particles 1. The number average particle diameter of the primary particles of the toner particles 1 was 6.5 μm.

< external addition step >

FM mixer with 7℃water in the jacket (FM 10C; from Nippon Coke)&In Engineering co., ltd.) 0.10 parts of silicone polymer particles 1 and 1.0 part of hydrophobic silica fine powder (BET specific surface area 150m ² Per g, obtained by hydrophobizing 100 parts of silica fine powder with 30 parts of Hexamethyldisilazane (HMDS) and 10 parts of simethicone) to 100.00 parts or more of the obtained toner particles 1.

When the water temperature in the jacket was stabilized at 7.+ -. 1 ℃ it was mixed with a rotating blade having a circumferential speed of 38m/sec for 5 minutes, thereby obtaining toner mixture 1.

The amount of water passing through the jacket is suitably adjusted during this process so that the temperature in the FM mixer tank does not exceed 25 ℃.

The resulting toner mixture 1 was sieved with a 75 μm mesh sieve, thereby obtaining toner 1. The production conditions and physical properties of toner 1 are shown in table 2.

< preparation examples of toners 2 to 17 and 25 to 33 and comparative toners 1 to 5 >

Toners 2 to 17 and 25 to 33 and comparative toners 1 to 5 were obtained as in the preparation example of toner 1, except that the conditions were changed as shown in table 2. The physical properties are shown in table 2.

< toner 18 preparation example >

< preparation example of toner particles 18 >

265 parts of the resin particle dispersion 1, 10 parts of the release agent dispersion and 10 parts of the colorant dispersion were dispersed with a homogenizer (Ultra-Turrax T50; manufactured by IKAJapan K.K.). This was stirred while the temperature in the vessel was adjusted to 30℃and 1mol/L aqueous sodium hydroxide solution was added to adjust the pH to 8.0.

An aqueous solution of 0.22 part of aluminum chloride dissolved in 10 parts of ion-exchanged water was added as a flocculant at 30 ℃ for 10 minutes under stirring. It was allowed to stand for 3 minutes before starting the temperature rise, and the temperature was raised to 50℃to produce a polymerAnd collecting particles. In this state with a "Multisizer ^TM The particle size of the aggregated particles was measured by 3 Coulter Counter "(manufactured by Beckman Coulter Inc.). When the weight average particle diameter reached 5.0. Mu.m, 0.9 parts of sodium chloride and 5.0 parts of Neogen RK were added to stop the particle growth.

1mol/L aqueous sodium hydroxide solution was added to adjust the pH to 9.0, and then the temperature was raised to 95℃to spheroidize the aggregated particles. When the average circularity reached 0.980, the temperature was reduced, and the mixture was cooled to room temperature, thereby obtaining toner particle dispersion 18.

Hydrochloric acid is added to the obtained toner particle dispersion 18 so as to adjust the pH to 1.5 or less, and the dispersion is stirred for one hour, left stand, and solid-liquid separation is performed with a pressure filtration unit, thereby obtaining a toner cake. This was reslurried with ion-exchanged water to obtain a dispersion again, and then solid-liquid separation was performed with the same filtration unit. The repulping and solid-liquid separation were repeated until the conductivity of the filtrate was 5.0 μs/cm or less, and then final solid-liquid separation was performed, thereby obtaining a toner cake. The resulting toner cake was dried, and then classified with a classifier, thereby obtaining toner particles 18. The number average particle diameter of the primary particles of the toner particles 18 was 4.5 μm.

The subsequent steps were performed as in the manufacturing example of toner 1, except that the conditions were changed as shown in table 2, to thereby obtain toner 18.

< toner 19>

< preparation example of toner particles 19>

An aqueous solution of 0.22 part of aluminum chloride dissolved in 10 parts of ion-exchanged water was added as a flocculant at 30 ℃ for 10 minutes under stirring. It was allowed to stand for 3 minutes before starting the temperature rise, and the temperature was raised to 50 ℃ to generate aggregated particles. At the positionIn the state by a Multisizer ^TM The particle size of the aggregated particles was measured by 3 Coulter Counter "(manufactured by Beckman Coulter Inc.). When the weight average particle diameter reached 5.5. Mu.m, 0.9 parts of sodium chloride and 5.0 parts of Neogen RK were added, thereby stopping the particle growth.

1mol/L aqueous sodium hydroxide solution was added to adjust the pH to 9.0, and then the temperature was raised to 95℃to spheroidize the aggregated particles. When the average circularity reached 0.980, cooling was started, and the mixture was cooled to room temperature, thereby obtaining toner particle dispersion liquid 19.

Hydrochloric acid was added to the obtained toner particle dispersion liquid 19 so as to adjust the pH to 1.5 or less, and the dispersion liquid was stirred for one hour, left to stand, and subjected to solid-liquid separation with a pressure filtration unit, thereby obtaining a toner cake. This was reslurried with ion-exchanged water to obtain a dispersion again, and then solid-liquid separation was performed with the same filtration unit. The repulping and solid-liquid separation were repeated until the conductivity of the filtrate was 5.0 μs/cm or less, and then final solid-liquid separation was performed, thereby obtaining a toner cake. The obtained toner cake was dried, and then classified with a classifier, thereby obtaining toner particles 19. The number average particle diameter of the primary particles of the toner particles 19 was 5.0 μm.

The subsequent steps were performed as in the production example of toner 1, except that the conditions were changed as shown in table 2, to thereby obtain toner 19.

< toner 20>

< preparation example of toner particles 20>

An aqueous solution of 0.22 part of aluminum chloride dissolved in 10 parts of ion-exchanged water was added as a flocculant at 30 ℃ for 10 minutes under stirring. It was allowed to stand for 3 minutes before starting the temperature rise, and the temperature was raised to 50 ℃ to generate aggregated particles. In this state use "Multisizer ^TM The particle size of the aggregated particles was measured by 3 Coulter Counter "(manufactured by Beckman Coulter Inc.). When the weight average particle diameter reached 10.2. Mu.m, 0.9 parts of sodium chloride and 5.0 parts of Neogen RK were added, thereby stopping the particle growth.

1mol/L aqueous sodium hydroxide solution was added to adjust the pH to 9.0, and then the temperature was raised to 95℃to spheroidize the aggregated particles. When the average circularity reached 0.980, the temperature was reduced, and the mixture was cooled to room temperature, thereby obtaining a toner particle dispersion 20.

Hydrochloric acid is added to the obtained toner particle dispersion 20 so as to adjust the pH to 1.5 or less, and the dispersion is stirred for one hour, left stand, and solid-liquid separation is performed with a pressure filtration unit, thereby obtaining a toner cake. This was reslurried with ion-exchanged water to obtain a dispersion again, and then solid-liquid separation was performed with the same filtration unit. The repulping and solid-liquid separation were repeated until the conductivity of the filtrate was 5.0 μs/cm or less, and then final solid-liquid separation was performed, thereby obtaining a toner cake. The obtained toner cake was dried and then classified with a classifier, thereby obtaining toner particles 20. The number average particle diameter of the primary particles of the toner particles 20 was 9.0 μm.

The subsequent steps were performed as in the manufacturing example of toner 1, except that the conditions were changed as shown in table 2, to thereby obtain toner 20.

< toner 21>

< preparation example of toner particles 21>

An aqueous solution of 0.22 part of aluminum chloride dissolved in 10 parts of ion-exchanged water was added as a flocculant at 30 ℃ for 10 minutes under stirring. It was allowed to stand for 3 minutes before starting the temperature rise, and the temperature was raised to 50 ℃ to generate aggregated particles. In this state with a "Multisizer ^TM The particle size of the aggregated particles was measured by 3 Coulter Counter "(manufactured by Beckman Coulter Inc.). When the weight average particle diameter reached 11.3. Mu.m, 0.9 parts of sodium chloride and 5.0 parts of Neogen RK were added, thereby stopping the particle growth.

1mol/L aqueous sodium hydroxide solution was added to adjust the pH to 9.0, and then the temperature was raised to 95℃to spheroidize the aggregated particles. When the average circularity reached 0.980, cooling was started, and the mixture was cooled to room temperature, thereby obtaining toner particle dispersion liquid 21.

Hydrochloric acid is added to the obtained toner particle dispersion 21 so as to adjust the pH to 1.5 or less, and the dispersion is stirred for one hour, left stand, and solid-liquid separation is performed with a pressure filtration unit, thereby obtaining a toner cake. This was reslurried with ion-exchanged water to obtain a dispersion again, and then solid-liquid separation was performed with the same filtration unit. The repulping and solid-liquid separation were repeated until the conductivity of the filtrate was 5.0 μs/cm or less, and then final solid-liquid separation was performed, thereby obtaining a toner cake. The obtained toner cake was dried and then classified with a classifier, thereby obtaining toner particles 21. The number average particle diameter of the primary particles of the toner particles 21 was 10.0 μm.

The subsequent steps were performed as in the manufacturing example of toner 1, except that the conditions were changed as shown in table 2, to obtain toner 21.

< preparation example of toner 22 >

< preparation example of toner particles 22 >

245 parts of the resin particle dispersion 1, 10 parts of the release agent dispersion and 10 parts of the colorant dispersion were dispersed with a homogenizer (Ultra-Turrax T50; manufactured by IKAJapan K.K.). This was stirred while the temperature in the vessel was adjusted to 30℃and 1mol/L aqueous sodium hydroxide solution was added to adjust the pH to 8.0.

An aqueous solution of 0.17 part of aluminum chloride dissolved in 10 parts of ion-exchanged water was added as a flocculant at 30 ℃ for 10 minutes under stirring. It was allowed to stand for 3 minutes before starting the temperature rise, and the temperature was raised to 50 ℃ to generate aggregated particles. The particle diameter of the aggregated particles was measured in this state with a "Multisizer TM 3 Coulter Counter" (manufactured by Beckman Coulter Inc.). When the weight average particle diameter reached 7.0 μm, 20 parts of the resin particle dispersion 1 was added as a surface layer resin (surface layer resin adding step).

Further, an aqueous solution of 0.05 part of aluminum chloride dissolved in 10 parts of ion-exchanged water was added over a period of 10 minutes. When the weight average particle diameter reached 7.2. Mu.m, 0.9 parts of sodium chloride and 5.0 parts of Neogen RK were added, thereby stopping the particle growth. 1mol/L aqueous sodium hydroxide solution was added to adjust the pH to 9.0, and then the temperature was raised to 95℃to spheroidize the aggregated particles. When the average circularity reached 0.980, the temperature was reduced, and the mixture was cooled to room temperature, thereby obtaining the toner particle dispersion liquid 22.

Hydrochloric acid is added to the obtained toner particle dispersion 22 so as to adjust the pH to 1.5 or less, and the dispersion is stirred for one hour, left stand, and solid-liquid separation is performed with a pressure filtration unit, thereby obtaining a toner cake. This was reslurried with ion-exchanged water to obtain a dispersion again, and then solid-liquid separation was performed with the same filtration unit. The repulping and solid-liquid separation were repeated until the conductivity of the filtrate was 5.0 μs/cm or less, and then final solid-liquid separation was performed, thereby obtaining a toner cake. The obtained toner cake was dried and then classified with a classifier, thereby obtaining toner particles 22. The number average particle diameter of the primary particles of the toner particles 22 was 6.5 μm.

The subsequent steps were performed as in the manufacturing example of toner 1, except that the conditions were changed as shown in table 2, to obtain toner 22.

< preparation example of toner 23 >

Toner 23 was obtained as in the manufacturing example of toner 22, except that resin particle dispersion 2 was used instead of resin particle dispersion 1 in the surface layer resin addition step.

< preparation example of toner 24 >

Toner 24 was obtained as in the manufacturing example of toner 22, except that resin particle dispersion 3 was used instead of resin particle dispersion 1 in the surface layer resin addition step.

TABLE 2

In the table, "c." means "comparison". R represents the ratio (B/A) of the number average particle diameter. X represents the content of metal element relative to 1g of the silicone polymer particles.

Example 1 ]

Toner 1 was evaluated as follows. The evaluation results are shown in table 3.

As an evaluation unit, a modified LBP 712Ci (manufactured by Canon inc.) was used. The processing speed of the main body was modified to 250mm/sec, and necessary adjustments were made so that an image was formed under these conditions. The toner was removed from the black box, and then 150g of toner 1 was filled.

(evaluation of developability)

< evaluation of durable fogging in high-temperature and high-humidity Environment >

Fogging was evaluated after continuous use in a high temperature and high humidity environment (30 ℃ C./80% RH). Paper Xerox4200 (75 g/m) ² The method comprises the steps of carrying out a first treatment on the surface of the Manufactured by Fuji Xerox co., ltd.) as evaluation paper.

The 15000 intermittent continuous use test was performed by outputting 2 letter E images with a printing rate of 1% every 4 seconds under a high-temperature and high-humidity environment.

Then, using a letter size of HP Brochure Paper g, glossy (basis weight 200 g/cm) in glossy paper mode (1/3 speed) ² ) A solid white image with a printing rate of 0% was printed as a transfer material. The fogging concentration (%) was calculated from the difference between the whiteness (white) of the transfer paper measured with "Reflectometer Model TC-6DS" (manufactured by Tokyo Denshoku Co., ltd.) and the whiteness of the white background portion of the printed output image, and the image fogging was evaluated.

An amber filter was used as the filter.

The smaller the value, the better the evaluation result. The evaluation criteria are as follows. Grades above C are considered good.

(evaluation criteria)

A: less than 1.0%

B: at least 1.0% and less than 2.0%

C: at least 2.0% and less than 3.0%

D: at least 3.0%

< evaluation of streak image in high-temperature high-humidity Environment >

The streak image is a vertical streak of about 0.5mm due to toner deterioration or contamination of a member by an external additive, and this image defect is easily observed when outputting the entire halftone image.

Fringe images were evaluated by: 15000 continuous use tests were first conducted under an environment similar to that of the fogging evaluation, and then a test was conducted on Xerox 4200 paper (75 g/m ² The method comprises the steps of carrying out a first treatment on the surface of the Manufactured by Fuji Xerox co., ltd.) and observing the presence or absence of streaks. Grades above C are considered good.

(evaluation criteria)

A: without streaking or toner patch

B: without speckled streaks, but with 1 to 3 small toner patches

C: with some spotty streaks at the edges, or 4 to 5 small toner patches

D: with speckled streaks across the surface, or with more than 5 small toner patches, or with distinct toner patches

< evaluation of toner bearing Member pollution in high temperature and high humidity Environment >

The toner bearing member is contaminated as an image defect in which the toner becomes fixed to the toner bearing member and contaminates the toner bearing member, causing the density of the halftone image to rise during long-term use.

Toner bearing member contamination was evaluated by: under the same environment as the fogging evaluation, 100 similar E letter images were first output, and then a sheet of paper (75 g/m in Xerox 4200 ( ² The method comprises the steps of carrying out a first treatment on the surface of the Manufactured by Fuji Xerox co., ltd.) on-screen halftone images were output and the density was measured. Then, a continuous use test was performed until 15000 sheets were reached, and the entire halftone image was output in the same manner, and And the concentration was measured. The change in density after 15000 sheets was calculated and outputted with 100 sheets of output as the initial density.

The image density was measured by measuring the relative density of the white background portion with respect to the image density of 0.00 according to the attached manual using a "Macbeth reflection density meter RD918" (manufactured by Gretag Macbeth), and taking the obtained relative density as an image density value. It was evaluated according to the following criteria, and a rating of C or higher was considered good.

(evaluation criteria)

A: a concentration increase of less than 5.0% relative to the initial halftone concentration

B: a concentration increase of at least 5.0% and less than 10.0% relative to the initial halftone concentration

C: a concentration increase of at least 10.0% and less than 15.0% relative to the initial halftone concentration

D: the concentration rise relative to the initial halftone concentration is at least 15.0%.

< evaluation of transfer efficiency in high-temperature high-humidity Environment >

As in the above fogging evaluation, the transfer efficiency was confirmed at the end of the durability evaluation. The toner carrying amount was set to 0.65mg/cm ² Is developed on a drum and then transferred to a Xerox 4200 paper (Xerox co.,75 g/m) ² ) Thereby obtaining an unfixed image. The transfer efficiency was then determined based on the mass change between the amount of toner on the drum and the amount of toner on the transfer paper (when all the toner on the drum was transferred to the transfer paper, the transfer efficiency was 100%). Grades above C are considered good.

A: transfer efficiency of at least 95%

B: transfer efficiency of at least 90% and less than 95%

C: transfer efficiency of at least 80% and less than 90%

D: transfer efficiency is less than 80%

< evaluation of image Density in high temperature and high humidity Environment >

As in the above fogging evaluation, the image density was confirmed at the end of the durability evaluation.

Paper for Xerox 4200 (Xerox Co.,75 g/m) ² ) Solid images were output on top, and image densities were measured.

A: an image density of at least 1.40

B: the image density is at least 1.30 and less than 1.40

C: the image density is at least 1.20 and less than 1.30

D: image density less than 1.20

< examples 2 to 33, comparative examples 1 to 5>

Toners 2 to 33 and comparative toners 1 to 5 were evaluated as in example 1. The evaluation results are shown in table 3.

TABLE 3

In the table, "c." means "comparative" and "c.e." means "comparative example".

While the invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.

Claims

1. A toner, comprising:

toner particles containing binder resin, and

characterized in that the toner particles contain a polyvalent metal compound,

the polyvalent metal compound is aluminum chloride,

the content of the aluminum element derived from the aluminum chloride in the toner particles is 0.080 mu mol/g to 0.400 mu mol/g,

the ratio of the number average particle diameter of the silicone polymer particles to the number average particle diameter of the toner particles is 0.0160 to 0.0650,

the content of the silicone polymer particles is at least 0.10 parts by mass relative to 100.00 parts by mass of the toner particles,

the organosilicon polymer particles have a structure in which silicon atoms and oxygen atoms are alternately bonded,

the silicone polymer has a structure represented by R ^a SiO _3/2 The structure of the T3 unit is shown,

wherein R is ^a Represent C _1-6 Alkyl or phenyl, and

at the silicone polymer particles ²⁹ In the Si-NMR measurement, the ratio of the area of the peak derived from the silicon having the T3 unit structure to the total area of the peaks derived from all silicon elements contained in the silicone polymer particles is 0.90 to 1.00.

2. The toner according to claim 1, wherein

The content of the aluminum element is 10 mu mol to 5000 mu mol with respect to 1g of the silicone polymer particles.

3. The toner according to claim 1 or 2, wherein

The content of the silicone polymer particles is 0.10 parts by mass to 5.00 parts by mass with respect to 100.00 parts by mass of the toner particles.

4. The toner according to claim 1 or 2, wherein

The content of the aluminum element is 20 mu mol to 400 mu mol with respect to 1g of the silicone polymer particles.

5. The toner according to claim 1 or 2, wherein

The silicone polymer particles have a number average particle diameter of 120nm to 350nm.

6. The toner according to claim 1 or 2, wherein

The toner particles contain an amorphous vinyl resin having an acid value of 1.0mg KOH/g to 40.0mg KOH/g on the surface of the toner particles.

7. The toner according to claim 1 or 2, wherein

The ratio of the number average particle diameter of the silicone polymer particles to the number average particle diameter of the toner particles is 0.0200 to 0.0500.